The present invention relates to antifoaming compositions and to intermediate anhydrous compositions.
Some industrial cleaning operations, such as the cleaning of bottles or cleaning in place, can result in the formation of a significant degree of foam. It is due in particular to the presence of food stains or of sticky residues present on the bottles. For the purpose of decreasing or even preventing the formation of this foam, it is known to add one or more defoaming surfactants to the cleaning composition. These defoaming surfactants are generally of the non-ionic type.
One of the subject-matters of the present invention consists of novel surfactant compositions which are derived from alkylpolyglycosides.
Alkylpolyglycosides are well-known non-ionic surfactants. Their manufacturing process is disclosed, for example, in Patent Application EP-A-0 077 167.
However, to date, it is impossible to use surfactant compositions based on alkylpolyglycosides which are devoid of water or devoid of fatty alcohol. This is because the very high melting temperatures of alkylpolyglycosides do not allow them to be handled in anhydrous form. They are therefore diluted in water or presented as a mixture with one or more fatty alcohols.
Patent Application EP-A-0 489 777 discloses antifoaming compositions comprising alkylpolyglycosides in which the alkyl chain comprises from 6 to 12 carbon atoms.
German Patent Application No. DE 38 35 199 discloses alkylpolyglycosides blocked by an arylmethyl or alkyl radical exhibiting antifoaming properties.
However, it is clear to a person skilled in the art that the blocking reaction employed in this publication cannot be applied to the many blocking reagents which decompose in water. In another aspect of the present invention, the Applicant Company has therefore sought to develop a novel blocking process which involves anhydrous intermediates which are devoid of fatty alcohols.
The subject-matter of the invention is therefore the composition (A) comprising:
a) at least one compound of formula (I)
(Z)yxe2x80x94(G)xxe2x80x94Oxe2x80x94RAxe2x80x83xe2x80x83(I) 
b) at least one compound of formula (II)
Zxe2x80x94Oxe2x80x94[CH2xe2x80x94CH(R1)xe2x80x94O]nxe2x80x94RBxe2x80x83xe2x80x83(II) 
c) optionally one or more compounds of formula (III)
(G)xxe2x80x94Oxe2x80x94RAxe2x80x83xe2x80x83(III), and 
d) optionally one or more compounds of formula (IV)
HOxe2x80x94[CH2xe2x80x94CH(R1)xe2x80x94O]nxe2x80x94RBxe2x80x83xe2x80x83(IV) 
such that the ratio by weight of the compound of formula (I) to the compound of formula (II) is between 0.1 and 10,
the ratio by weight: compound of formula (III)/compound of formula (I) is between 0 and 1, and
the ratio by weight: compound of formula (IV)/compound of formula (II) is between 0 and 1, in which formulae (I), (II), (III) and (IV):
Z represents:
either a xe2x80x94CH(CH3)xe2x80x94Oxe2x80x94R2 group, in which R2 represents a saturated or unsaturated, linear or branched, aliphatic hydrocarbon-comprising radical comprising from 1 to 30 carbon atoms,
or a xe2x80x94CH2xe2x80x94CH(OH)xe2x80x94R3 radical, in which R3 represents a linear or branched alkyl radical comprising from 1 to 4 carbon atoms;
y represents a decimal number of greater than 0 and less than or equal to 3x+1;
x represents a decimal number of between 1 and 5;
n is an integer of between 1 and 30;
R1 represents a hydrogen atom or a methyl radical;
G represent the residue of a saccharide;
RA and RB represent, independently of one another, a saturated or unsaturated, linear or branched, hydrocarbon-comprising radical comprising from 1 to 30 carbon atoms.
When Z represents a xe2x80x94CH(CH3)xe2x80x94OR2 group, it is in particular the 1-methoxyethyl, 1-ethoxyethyl, 1-propoxyethyl, 1-isopropoxyethyl, 1-butoxyethyl, 1-isobutoxyethyl, 1-(pentyloxy) ethyl, 1-(dodecyloxy)-ethyl or 1-(octadecyloxy)ethyl radical.
When Z represents a xe2x80x94CH2xe2x80x94CH(OH)xe2x80x94R3 radical, it is in particular the 2-hydroxybutyl radical.
The term xe2x80x9csaturated or unsaturated, linear or branched, hydrocarbon-comprising radical comprising from 1 to 30 carbon atomsxe2x80x9d denotes in particular, for RA and/or RB, alkyl radicals or alkenyl radicals.
The term xe2x80x9cresidue of a saccharidexe2x80x9d denotes, for G,a polyvalent radical resulting from the removal from a sugar molecule, on the one hand, of a hydrogen atom of a hydroxyl group and, on the other of the anomeric hydroxyl group.
The term xe2x80x9csaccharidexe2x80x9d denotes in particular glucose or dextrose, fructose, mannose, galactose, altrose, idose, arabinose, xylose, ribose, gulose, lyxose, sucrose, maltose, maltotriose, lactose, cellobiose, dextran, talose, allose, raffinose, levoglucosan, cellulose or starch.
The oligomeric structure (G)x can exist in any isomeric form, whether relating to optical isomerism, geometrical isomerism or positional isomerism; it can also represent a mixture of isomers. In the formulae (I) and (III) as defined above, the Oxe2x80x94RA group is bonded to G via the anomeric carbon, so as to form an acetal functional group.
In the definitions of the formulae (II) and (IV), the xe2x80x94[CH2xe2x80x94CH(R1)xe2x80x94O]n group indicates that it can be either a chain composed solely of ethoxyl groups (R1xe2x95x90H) or a chain composed solely of propoxyl groups (R1xe2x95x90CH3) or a chain composed of both ethoxyl and propoxyl groups. In the latter case, the xe2x80x94CH2CH2O and xe2x80x94CH2xe2x80x94CH(CH3)xe2x80x94O fragments are distributed in a block or random manner.
In the formula (I) as defined above, the Z group or groups are bonded to (G)x via an oxygen atom of one of its hydroxyl functional groups.
When, in the composition as defined above, there are several compounds of formulae (I), (II), (III) and/or (IV), they are distinguished from one another by the definitions of RA and RB and, optionally, in the case of products of formula (I), by the values of y.
In a first preferred alternative form of the present invention, G represents the glucose residue, x, which represents the mean degree of polymerization of the saccharide, is between 1.05 and 2.5 and in particular between 1.1 and 2.0, and y is less than or equal to 2.
The composition as defined above in which the ratios by weight: compound of formula (III)/compound of formula (I) and compound [lacuna] (IV)/compound of formula (II) are equal to 0 constitutes a second preferred alternative form of the present invention; in this case, the composition therefore comprises neither compound of formula (III) nor compound of formula (IV).
In a third preferred alternative form of the present invention, n is less than or equal to 15 in the formulae (II) and (IV).
In a fourth preferred alternative form of the present invention, in the formulae (I), (II), (III) and (IV), RA and RB comprise, independently of one another, from 6 to 18 carbon atoms and represent in particular a hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, octadecenyl, octadecadienyl or octadecatrienyl radical, the said radicals being linear or branched.
In a fifth preferred alternative form of the present invention, in the formulae (I) and (II), Z represents a 1-(octadecyloxy)ethyl, 1-isobutoxyethyl or 2-hydroxybutyl group.
A particular subject-matter of the invention is the composition as described above, comprising one or more compounds of formula (I), one or more compounds of formula (II), optionally one or more compounds of formula (III) and optionally one or more compounds of formula (IV), in which composition, in the formulae (I), (II), (III) and (IV), the substituents RA and RB are identical and represent an octyl, nonyl, decyl or 2-ethylhexyl radical.
Another subject-matter of the invention is a process for the preparation of the composition (A) as defined above, characterized in that the sugar of formula (V)
Hxe2x80x94Gxe2x80x94OHxe2x80x83xe2x80x83(V) 
is reacted in acidic medium with an excess of at least one alcohol of formula (VI)
HOxe2x80x94RAxe2x80x83xe2x80x83(VI) 
one compound of formula (III) and the mixture in excess of at least one alcohol of formula (VI), to which mixture (B) is added at least one compound of formula (IV) in a ratio by weight of compounds of formula (III) to compounds of formula (IV) of between 0.1 and 10, in order to form a mixture (C), which mixture is neutralized and then subjected to a distillation stage in order to remove the excess alcohol of formula (VI) and thus to form the anhydrous composition (D) comprising at least one compound of formula (III) and at least one compound of formula (IV), which anhydrous composition (D) is reacted with a compound of formula (VII)
Zxe2x80x2xe2x80x94Axe2x80x83xe2x80x83(VII) 
capable of reacting with one or more hydroxyl functional groups of the (G)x group, in order to result in the composition (A).
In an alternative form of the process described above, when RA represents the radical derived from a fatty alcohol, the compound of formula (III) can be obtained by first preparing an alkylpolyglycoside with a light alcohol, such as methanol or butanol, by etherification of the corresponding saccharide, and then, in a second stage, by carrying out a transetherification with the alcohol of formula (VI) and by distilling off the light alcohol.
The term xe2x80x9ccompound of formula (VII)xe2x80x9d denotes in particular epoxides, such as, for example, butylene oxide, or alkyl vinyl ethers, such as, for example, isobutyl vinyl ether or octadecyl vinyl ether.
In a preferred alternative form of the process as described below, the substituents RA and RB are identical.
In another preferred alternative form of the process as described above, the glucose is mixed [sic] with a fatty alcohol fraction corresponding to a mixture of alcohols of formula (VI), in order to form the corresponding mixture (B1) of alkylpolyglucosides of formula (III1), corresponding to compounds of formula (III) in which G represents the glucose residue, and of the excess of the fatty alcohol fraction, to which mixture (B1) is added a mixture of alkoxylated compounds of formula (IV1), prepared from the same fatty alcohol fraction, in a ratio by weight of compounds of formula (III1) to compounds of formul (IV1) of between 0.2 and 5, in order to form a mixture (C1), which mixture is neutralized and then subjected to a distillation in order to form the anhydrous composition (D1) comprising a mixture of compounds of formula (III1)
(G1)xxe2x80x94Oxe2x80x94RAxe2x80x83xe2x80x83(III1), 
in which G1 represents the glucose residue, and a mixture of alkoxylated compounds of formula (IV1)
HOxe2x80x94[CH2xe2x80x94CH(R1)xe2x80x94O]nxe2x80x94RAxe2x80x83xe2x80x83(IV1), 
which anhydrous composition (D1) is reacted with an alkyl vinyl ether in order to form the composition (A1) comprising:
a) a mixture of compounds of formula (II)
[R2xe2x80x94Oxe2x80x94CH(CH3)]yxe2x80x94[(G1)xxe2x80x94Oxe2x80x94RA]xe2x80x83xe2x80x83(I1) 
b) a mixture of compounds of formula (II1)
R2xe2x80x94Oxe2x80x94CH(CH3)xe2x80x94Oxe2x80x94[CH2xe2x80x94CH(R1)xe2x80x94O]nxe2x80x94RAxe2x80x83xe2x80x83(II1) 
c) optionally a mixture of compounds of formula (III)
(G1)xxe2x80x94Oxe2x80x94RAxe2x80x83xe2x80x83(III1), and 
d) optionally a mixture of compounds of formula (IV1)
HOxe2x80x94[CH2xe2x80x94CH(R1)xe2x80x94O]nxe2x80x94RAxe2x80x83xe2x80x83(IV1). 
In another preferred alternative form, D1 is reacted with butylene oxide in order to give the final composition (A2) comprising:
a) a mixture of compounds of formulae [sic] (I2)
[CH3xe2x80x94CH2xe2x80x94CH(OH)xe2x80x94CH2]yxe2x80x94[(G1)xxe2x80x94Oxe2x80x94RA]xe2x80x83xe2x80x83(I2) 
b) a mixture of compounds of formulae [sic] (II2)
CH3xe2x80x94CH2xe2x80x94CH(OH)xe2x80x94CH2xe2x80x94Oxe2x80x94[CH2xe2x80x94CH(R1)xe2x80x94O]nxe2x80x94RAxe2x80x83xe2x80x83(II2) 
c) optionally a mixture of compounds of formula (III1)
(G1)xxe2x80x94Oxe2x80x94RAxe2x80x83xe2x80x83(III1), and 
d) optionally a mixture of compounds of formula (IV1)
HOxe2x80x94[CH2xe2x80x94CH(R1)xe2x80x94O]nxe2x80x94RAxe2x80x83xe2x80x83(IV1). 
The compounds of formula (VI) are known to a person skilled in the art and are commercially available. The fatty alcohol fractions are also for their part known to a person skilled in the art; some are commercially available or can be obtained according to conventional methods from natural fats or oils, such as, for example, coconut oil, palm kernel oil, palm oil, soybean oil, rapeseed oil, castor oil, beef tallow or herring oil.
The alkoxylated compounds of formulae [sic] (IV) are commercially available or obtained by the action of ethylene oxide and/or propylene oxide on the corresponding alcohols, according to conventional methods known to a person skilled in the art.
Another subject-matter of the invention is the anhydrous composition (D) and in particular the anhydrous composition (D1) which are intermediates in the process and in its alternative form which are described above.
The composition (A) which is a subject-matter of the invention is surface active and it also exhibits advantageous antifoaming properties. This property makes it possible to use it in many types of industry.
In the farm-produce industry, these products can be used in the cleaning and disinfecting of containers which may be in contact with foodstuffs; they can also be used as antifoaming agent in the extractive farm-produce industries, such as sugar refineries or starch manufacturing plants, in the fermentation industries, such as plants for production of amino acids, organic acids or enzymes, and in the livestock fodder industries.
The composition (A) according to the invention can generally be used in the cleaning of hard surfaces.
Finally, these products can be used in detergent formulations for household use, such as domestic cleansing products.
Each of the uses mentioned above represents in itself an aspect of the present invention.
An antifoaming composition according to the invention can be provided in a concentrated form or in a dilute form which is ready for use.
When it is provided in a concentrated form, it can comprise from 5 to 70% by weight of at least one compound of formula (I) and from 5 to 70% by weight of at least one compound of formula (II).
When it is provided in a dilute form, it can comprise from 0.004% to 20% by weight of at least one compound of formula (I) and from 0.004% to 20% by weight of at least one compound of formula (II).
The intermediate compositions (D) and (Dl) of the process are surface active in themselves and can also be used for this property in dilute or ready-for-use form, as is described for the composition (A).
According to another aspect of the invention, a cleaning composition comprises from 2 to 50% by weight of one or more alkaline agents, such as, for example, sodium hydroxide or potassium hydroxide, and between 0.001 and 10% by weight of the composition (A) as defined above.
The following examples illustrate the invention without, however, limiting it.